Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
  • C10M151/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/06—Mixtures of thickeners and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/06—Perfluoro polymers
  • C10M2213/0606—Perfluoro polymers used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/041—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2221/043—Polyoxyalkylene ethers with a thioether group
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Semi-solids; greasy

Definitions

• the present invention relates to fluorinated additives to be used as stabilizing agents to thermooxidation for fluorinated lubricating oils and greases.
• the products of the invention can also be used as fluorinated lubricating oils having a high thermooxidative stability.
• the invention relates to oligomeric products having a (per)fluoropolyether structure containing pyridine rings in the polymeric backbone.
• the products according to the present invention can be used as oil and grease additives and also as lubricating oils self-stabilized at high temperature, higher than 200°C, generally higher than 230°C, preferably higher than 250°C, still more preferably higher than 300°C, and even up to 330°C, in oxidizing environment, optionally in the presence of metals.
• the invention additives are obtainable with a process having very high yields, preferably higher than 90%.
• perfluoropolyethers have high thermal stability and are therefore used as lubricants, oils or greases, or as hydraulic fluids in many applications under severe working conditions, up to temperatures of about 200°C, in oxidative environment, optionally in the presence of metals.
• perfluoropolyethers when used at temperatures higher than 200°C, for example 230°-250°C, do not show a high thermooxidative stability, until reaching the complete decomposition of the oil.
• the thermal decomposition process causes the breakage and fragmentation of the perfluoro-poly-ether chains of the lubricating compound. In some cases the total decomposition of the perfluoropolyether fluid takes place. Under these conditions volatile fractions are formed, which evaporate, so that the lubricant is totally lost.
• the lubricant decomposition is generally associated with a progressive metal corrosion in contact with the fluid.
• additives described in the prior art contain perfluoropolyether chains linked to phosphotriazine groups. See for example USP 5,326,910. These products have a good thermooxidative stability. However the yields in said additives are low.
• Other additives described in the prior art contain perfluoropolyether chains linked to phosphazene groups (aryl substituted). See for example EP 597,369. These compounds have a good thermooxidative stability. Also in this case the yields in these additives are low, furthermore rather complex process conditions are used, as inert environment, flammable and volatile anhydrous solvents; furthermore sodium hydride is used.
• thermooxidative stabilizing additives of the prior art are prepared by multistep processes. It is often necessary to prepare intermediate compounds by complicated syntheses and sometimes the intermediates isolated during the synthesis are toxic. Furthermore the yields are low. This represents a drawback from an industrial point of view. Besides, the starting compounds used in the synthesis of some additives described in the prior art, as for example the phosphazene precursor, are expensive compounds and represent an additional cost of the industrial process.
• the Applicant has surprisingly and unexpectedly found products having (per)fluoropolyether structure which solve the above technical problem, i.e. usable as additives of perfluoropolyether oils or greases, or as oils per se, without the need to add thermooxidative stabilizers.
• An object of the present invention are compounds having the following formula: wherein:
• Rf the repeating unit (C 3 F 6 O) of the (per)fluoro-polyoxyalkylene chain can be: -(CF 2 CF(CF 3 )O)- or -(CF(CF 3 )CF 2 O)-.
• the preferred perfluoropolyether chain Rf is selected from the following structures:
• Particularly preferred structures are (A) and (B), more preferably (B).
• the compounds of the present invention are transparent and odourless viscous liquids.
• the compounds of the present invention can also be used as lubricating oils. It has been indeed surprisingly and unexpectedly found by the Applicant that the compounds of the present invention have a high thermal stability at temperatures higher than 200°C, generally higher than 230°C, preferably higher than 250°C, still more preferably higher than 300°C, and even up to 330°C, optionally in the presence of metals.
• the compounds of formula (I) can also be used as additives of fluorinated lubricants, oils and/or greases, to confer improved thermooxidative properties.
• a further object of the present invention are lubricating compositions comprising:
• the perfluoropolyethers of the classes from (1) to (7) are liquids having a very low vapour pressure and have a kinematic viscosity measured at 20°C generally from 10 to 10,000 cSt, preferably from 300 to 2,000 cSt.
• the preferred perfluoropolyether oils are those of the classes (1), (4), (5) and are available on the market with the trademark FOMBLIN® marketed by Solvay Solexis.
• oils of formula (I) and the formulations of the invention, wherein the compounds of formula (I) are used as additives for fluorinated oils and greases can contain other additives commonly used in the formulations of lubricants having a perfluoropolyether structure.
• additives commonly used in the formulations of lubricants having a perfluoropolyether structure.
• anti-wear, anti-rust additives and Lewis anti-acid additives can be mentioned.
• usable anti-wear additives are those having a perfluoropolyether base linked to phosphazene rings, as for example those described in EP 1,336,614 in the name of the Applicant.
• the formulations contain one or more perfluoropolyether oils, belonging to one or more of the above classes, and thickening additives, preferably PTFE, optionally sodium terephthalate, calcium or lithium soaps, polyurea.
• thickening additives preferably PTFE, optionally sodium terephthalate, calcium or lithium soaps, polyurea.
• Other components, generally contained in the greases, are the following: dispersing agents as for example surfactants, in particular nonionic surfactants and preferably with a perfluoropolyether or perfluoroalkyl structure; besides talc or inorganic fillers.
• a further object of the present invention is a process for obtaining the compounds of formula (I), said process comprising the following steps:
• step a) The compounds of formula (II) used in step a) are known in the prior art, for example they can be prepared as described in USP 3,810,874.
• step a) compound (II)/compound (III) molar ratio ranges from 1 to 2. Preferably the ratio in equivalents compound (II)/base is equal to 1.
• the bases which can be used are inorganic bases, selected for example between KOH and NaOH, or organic bases as for example potassium terbutylate, aliphatic amines, as for example triethylamine.
• the organic solvent optionally used in the process of the present invention is preferably selected from hydrogenated solvents, as for example terbutyl alcohol, acetonitrile, diglyme, DMF, toluene, xylene, or fluorinated or hydrofluorinated solvents, having boiling point between 20°C and 150°C, preferably between 60°C and 100°C.
• hydrogenated solvents as for example terbutyl alcohol, acetonitrile, diglyme, DMF, toluene, xylene, or fluorinated or hydrofluorinated solvents, having boiling point between 20°C and 150°C, preferably between 60°C and 100°C.
• the yields of compound (IA) obtained at the end of step b) are high and higher than 80%, preferably higher than 90%.
• step a) and in step c) the reaction times are between 8 and 24 hours.
• step c) compound (IA)/substituted mono-halogen aroamtic compound ratio by equivalent ranges from 2 to 1, preferably 1.
• the (per)fluoropolyether compounds of the present invention can be used as additives in compositions of oils and greases, and generally of perfluoropolyether-based lubricating fluids. They have the property of stabilizing perfluoropolyether oils and greases in thermooxidative environment even at use temperatures higher than 200°C, generally higher than 230°C, preferably higher than 250°C, still more preferably higher than 300°C, and even up to 330°C, also in the presence of metals. Besides, said additives show an extremely reduced vapour pressure, comparable or even lower than that of the perfluoropolyether lubricating oil. Therefore when the application conditions require high temperatures, even by operating under reduced pressures, no substantial loss of additive by evaporation is noticed. Therefore the lubricating formulation remains substantially unaltered assuring the performance in use for a long time.
• the compounds of the present invention can also be used as lubricaing oils having a high thermal stability, therefore capable to be used at high temperatures, generally higher than 200°C up to 330°C, in thermooxidative environment also in the presence of metals.
• the invention compounds of formula (I), as above said, when used as lubricaing oils have the advantage not to require the addition of specific stabilizing additives at thermooxidation. This is unexpected and surprising as for the lubricating oils of the prior art it is always required the addition of thermooxidative stabilizers when the oils are used at high temperatures in oxidative environment, for example in air.
• the compounds of the present invention are obtainable with a simple process, in high yields, as said higher than 80%, preferably higher than 90%, and which allows to prepare oils even having a high molecular weight, as required for many applications.
• thermooxidation test has been carried out by using the equipment described by Carl E. Snyder, Jr. and Ronald E. Dolle, Jr., in ASLE Transactions, 13(3), 171-180 (1975).
• the used operating conditions were the following:
• a sample of the fluid to be tested containing the additive excluding the comparative Examples carried out with the non additived fluid, is introduced in the glass test tube of the equipment (see for example Fig. 1 of the reference). It is weighed and heated at the test temperature. The required time elapsed, the glass test tube is cooled to room temperature and weighed again. The difference of weight before and after heating, referred to the weight of the sample before the test, gives the percent weight loss of the tested fluid. At the end of the test the state of the metals dipped into the fluid is visually evaluated.
• the ASTM D 4172 method has been used as application test allowing to determine the wear as described hereinafter.
• a fourth sphere of the same kind, connected to an electric motor which allows its rotation, is placed over the three mentioned spheres with a charge of 40 ⁇ 0.2 kgf (392 N). The whole is assembled, closed and heated to 75° ⁇ 2°C.
• the fourth sphere placed on the three of reference, is rotated at the rate of 1200 ⁇ 60 rpm for 60 ⁇ 1 minutes.
• the container is disassembled, the lubricant is removed and the wear of the three spheres contained therein is evaluated by an optical microscope having a 0.01 mm precision.
• the wear value expressed in mm, is obtained as an arithmetic average of six determinations, by measuring for each sphere, without removing it from the hollow, the wear diameter in the rotation direction and the diameter perpendicular thereto.
• the number average molecular weight is determined by 19 F NMR analysis according to S. Turri et al. Macromolecules, 1995, 28, 7271-7275 and S. Turri et al. Macromol. Chem. Phys. 198 3215-3228 (1997).
• the viscosity index is determined according to the ASTM D 2270 method determining the kinematic viscosities at 20°C, 40°C and 100°C.
• thermogravimetric analysis has given the following results, expressed in loss per cent by weight: nitrogen: 1%, 242°C; 2%, 275°C; 10%, 378°C; 50%, 477°C.
• the organic phase is anhydrified by stripping at 120°C at a residual pressure of 10 -2 mbar for about 4 hours, and then filtered on 0.2 ⁇ m PTFE filter. 27.5 g of product are obtained.
• thermogravimetric analysis has given the following results, expressed in loss per cent by weight: nitrogen: 1%, 245°C; 2%, 275°C; 10%, 378°C; 50%, 469°C.
• thermogravimetric analysis has given the following results expressed in loss per cent by weight: nitrogen: 10%, 269°C; 50%, 455°C.
• a perfluoropolyether oil Fomblin® Z25 is additioned with an amount equal to 1% (w/w) of the compound of the Example 2.
• Fomblin® Z25 is additioned with an amount equal to 1% (w/w) of the compound of the Example 2.
• the above thermooxidation test is carried out. After 250 h at 270°C a weight loss of the additived lubricant equal to 1.4% by weight is determined.
• the metals dipped into the fluid during the test did not show oxidation/attack signs; at the end of the test their aspect was comparable with that of the specimens of the same metals not subjected to the treatment. Stability to Lewis acids
• a perfluoropolyether oil Fomblin® Z25 is additioned with an amount equal to 1% (w/w) of the above prepared compound.
• the stability test to Lewis acids is carried out according to the method described hereinafter. 5 grams of the composition oil + additive together with 0.1 g of AlF 3 are fed into a glass test tube (about 10 cc). The test tube is weighed and closed with a screw plug having a hole in the middle on which a 30 cm PTFE little pipe is fixed which conveys possible decomposition products in a NaOH solution (0,1 N), contained in a gathering cylinder. The test tube is weighed and then heated at 250°C for 24 hours. At the end the test tube is cooled and weighed again.
• the weight loss calculated as difference of the sample weight before and after heating, referred to the sample weight before heating, is equal to 0.65% by weight.
• the Example 8 was repeated but at 300°C for 24 hours. It has been found that the weight loss is of 2.0%.
• the compound synthesized in the Example 2 is subjected to the above described thermooxidation test. After 250 h at 270°C a weight loss of the compound of 1.0% by weight is noticed.
• a perfluoropolyether oil Fomblin® Z25 is additioned with an amount equal to 1% (w/w) of the compound of the Example 7.
• a wear value equal to 1.16 mm is determined.
• Example 12 is repeated but omitting the additive. In this case a wear value equal to 1.50 mm is determined.
• the presence of the additive according to the present invention has allowed to reduce the wear value of about 23%.
• the products obtained in the Examples 2, 3 were characterized as regards the viscosity at three different temperatures: 20°, 40° and 100°C, and compared with a perfluoropolyether oil Fomblin® M60.
• a perfluoropolyether oil Fomblin® Z25 is additived with an amount equal to 1% (w/w) of the compound of the Example 6.
• the above described thermooxidation test is carried out. After 250 h at 270°C a weight loss of the additived lubricant equal to 1.3% by weight is determined.
• the metals dipped into the fluid during the test did not show oxidation/attack signs; at the end of the test their aspect was comparable with that of the specimens of the same metals not subjected to the treatment.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
• Polyethers (AREA)

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